Refining of fixed gases



March 17, 1936. r. r. GRAY REFINING OF FIXED GASES 1 Filed may 19, 1930 origina y, INVENToR,

pra-Ass, s y

By Exeem-MS,

ATTORNEY. l

55 This apparatus cia treating tower It l Patented Mar. -1 7, 1936 UNITED STATES assists a nEFmlNG or'. FIXED casEs Thomas T. Graymooeased, into of Elizabeth, N. J., by Theodore S. Kenyon, Summit, N. J., and Union County Trust Company, Elizabeth, N. J.,

executors, assignors to The Gray Processes Corporation, Newark, N. J., a corporation of Dela- Ware continuation or application serial No. 453,637, May 19, 193i). This application July 24, 1934,

Serial No. 136,676

This application-.is a continuation o! the copending application Serial No. 453,637, ill'ed May- 19, 1930, which-is a continuation-impart of' the application Serial No. 664,893, filed September s 26, 1923, patented May 20, 1930 as Patent No.

This invention relates to the rening of fixed gases occurring naturally in petroleum or resulting from the processing of'petroleum'in the .0 renery and has for an object the recovery from such xed gases of hydrocarbons lying in the Vgasoline boiling range.

It is quite old in the art to recover gasoline as a liquid from natural gas or from fixed gas l5 resulting from the distillation or cracking of petroleum. However, in previous methods, there has been accomplished mereLv the,removal 4of hydrocarbons which, under ordinary conditions and by themselves are liquid, but are carried bin a great amount of iixed gas. Thse compounds .n arenow removed from :Ilxed gases by several methods or combinations of methods, but the usual method is compression followed by solution in a liquid. In all these methods, only normally liquid hydrocarbons carried in the xed gas are removed -and there is no alteration of chemical constitution of any part of the xed gas. According `to the present invention, certain unstable, unsaturated compounds which may be of thedioleiln or related types contained in e xed gas are polymerized by the action of a solid adsorptive material to other compounds of totally.

diiierent physical and chemical properties. These new compounds lie within the gasollne boiling range and are liquid at ordinary conditions ot temperature and pressure and thus difier from the xed gases from which they were ,formedp Fixed gases of the character above referred to maybe contacted with solid adsorptive4 material separately or may be contacted siinultaneously-with cracked gasoline vapors, in themanuiacture of which by cracking the xed gases are produced and which contain unstable, unsaturated compounds which tend to 'discoloron exposureto light .and to form deposits, there-o by-increasing the yield o! gasoline trom such valpors. Also, the method may be used to increase the 'yield in cracking processes oi the type which produce gasoline ofsuch color. and stability that it does not need to be subjected to decolorization treatment. A The accompanying drawing discloses one form of apparatus which may be used -for practicing the invention.

' bottom of the tower.

preferably equipped with a layer v`II`of heatinsulating material. Within the tower there'isprovided a conical uid permeableshelf I2 terminating in a discharge spout I3 controlled by a valve I4. On the shelf I2 is supported acharge 5 I5 of solid adsorptivematerial, the shelf I2 being impervious to such material. yA manhole I6 closed by a cover` I1 is provided for introducing the solid adsorptive vmaterial into the. treating tower. Avapor inlet pipe I8 controlled by a lo valve I9 communicates with the upper part of the tower and a vapor outlet pipe 2l) controlled by a valve' 2i leads from'the treating tower'at a point below the shelt I2. A trapped drainage pipe 22 controlledby valve 23 leadsirom the Fixed gases 'or ilxed gases combined with 'cracked hydrocarbon vapors'are introduced into the treating tower I0 through the pipe I8 and are caused to pass through the solid adsorptive material I5 and are then conducted by' the pipe 20 to a condenser (not shown). `During the passage or the fixed gases tmougnthe sona ad;

sorptive material, certain reactive unstable, ,un-

saturatedl constituents are polymerized into com- 25 pounds lying in the gasoline boiling range. .The cracked vapors are rened by the solid adsorpe tive material as described in, the .Patent No. 1,340,889 and application, Serial'Nm 664,893. A suitable -solid vadsorptive material is fullers earth, but other adsorptive material having similar selective polymerizing. characteristics'may be used. The polymerization of the unstable, unsaturated hydrocarbons in the fixed gases re'- sults in an increased yield of gasoline in are' 35 lining process. wherein cracked Ahydrocarbons mixed with fixed gases produced in the cracking operation are. rened-by -bein'g passed through a bed of solid adsorptive material. l The fixed gases, after passage treating material, may still carry some polymerized gasoline which is not liquefied d ue to the vapor pressure oi the remaininggases. This gasoline may be recovered from thegases by any of thewell-known compression or adsorp- 45- tion" processes. T f

Althoughthe process has been described by reference -to xed gas from cracking processes having -as theirobject the production of gasoline.

it may also be' practiced in connection with the 50 cracking o f oil to gas. Injsuch cases, the cracked gas, such'as is intended for use in e 1ching ter and the 1ike,'is treated in ithe m ner slfwn.

Unstable, unsamnatea compounds 1n the genre polymerized liquids-in the' gasoline boiling 55 through the 40 w re-run still. \The process is not limited to any particular stateof conditions and the invention is limited only by the scope of the appended claims. 'When treating ilxed gas mixed with gasoline vapors, the temperature and pre ure are 20 preferably those best suited tothe trea ment of the .latter and are llbrium boiling point o pressure between atmospheric and 500 square inch or more. When treating fixed gas separately, thertemperature and pressure may be varied over a wide range, depending on the nature of the unsaturatedcompounds present and the amount of polymerization desired. With highly reactive im'saturated compounds atmospheric pressure and normal temperature will bring about conversion. For less reactive unsaturated compounds 'higher pressures, even as high as 100 atmospheres and higher and temperatures of the order of'650" F. and above, 'will'fre'quently' be foundadvisable. 'What i s clamed.ls:"

l. 'Ihe process of obtaining valuable low-boiling normally liquid hydrocarbons suitable for use `f as motonfuel from hydrocarbon gases contain' 40 lng gaseous unsaturated hydrocarbons, which comprises continuously passing a stream'oi` said gasesin the absence of added oxygen in contact with solid adsorbent catalytic material .at an elethe mixture and at a usuaflly at or near the equlaos-1,575

vated temperature and pressure for' a sunicient period of time to effect a polymerization of said gaseous imsaturated hydrocarbons to normally liquid products, removing the treated stream of gases and products from the catalytic materialvv drocarbons to normally liquid products, removing the treated stream of gases and products from the bed of fullerjs earth and recovering said normally liquid products from the remaining unconpounds peg Verted hydrocarbon gases.

h 3. The process of obtaining. valuable low-boiling normally liquid hydrocarbons suitable for use as motor-fuel from hydrocarbon gases containing gaseous unsaturated hydrocarbons, which comprises continuously passing astream oi.' sa/idJgases in contact with solid adsorbent catalytic material at an elevated temperature and pressure for a suillcient period of time to eiect apolymerization -oi' said gaseous unsaturated hydrocarbons to normally liquid products, removing the treated stream ofgases and products from the catalytic materialfand recovering said normally liquid products from the remaining unconverted hydrocarbon gases.

'IHEoDQRfEs KENYON. UNION COUNTY TRUST COMPANY, -By C. MCK. WHI'I'I'EMORE,

' a President. Ezecutors of the Estqtaof ThomasT. Grail, De-v 

